EP0712659B1 - Wasser-absorbent, verfahren zu dessen herstellung und den enthaltender absorbent-gegenstand - Google Patents

Wasser-absorbent, verfahren zu dessen herstellung und den enthaltender absorbent-gegenstand Download PDF

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Publication number
EP0712659B1
EP0712659B1 EP95921136A EP95921136A EP0712659B1 EP 0712659 B1 EP0712659 B1 EP 0712659B1 EP 95921136 A EP95921136 A EP 95921136A EP 95921136 A EP95921136 A EP 95921136A EP 0712659 B1 EP0712659 B1 EP 0712659B1
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EP
European Patent Office
Prior art keywords
absorbing agent
weight
agent
crosslinking agent
absorbing
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EP95921136A
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English (en)
French (fr)
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EP0712659A4 (de
EP0712659A1 (de
Inventor
Katsuyuki Wada
Kinya Nagasuna
Shin-Ichi Fujino
Yoshihiko Masuda
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15203—Properties of the article, e.g. stiffness or absorbency
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • the present invention relates to an absorbing agent suited for use in sanitary goods such as paper diaper (disposable diaper), sanitary napkin, incontinence pad, etc., and a method of manufacturing the same and also relates to an absorbent product containing such absorbing agent.
  • an absorbent resin is widely used in sanitary goods such as paper diaper, sanitary napkin, incontinence pad, etc., for the purpose of absorbing liquid.
  • absorbent resins examples include: a partially neutralized crosslinked polymer of polyacrylic acid (Japanese Laid-Open Patent Publication No. 84304/1980 (Tokukaisho 55-84304), Japanese Laid-Open Patent Publication No. 108407/1980 (Tokukaisho 55-108407) and Japanese Laid-Open Patent Publication No. 133413/1980 (Tokukaisho 55-133413)); a hydrolyzed graft polymer of starch-acrylonitrile (Japanese Examined Patent Publication No. 43995/1974 (Tokukosho 46-43995)); a neutralized graft polymer of starch-acrylic acid (Japanese Laid-Open Patent Publication No.
  • the absorbent resin include absorbing capacity and absorbency under pressure when it is in contact with an aqueous liquid like a body fluid, gel strength, and absorbing power of absorbing liquid from a base material containing an aqueous liquid, etc.
  • the absorbent resins having some of the above-mentioned properties which show desirable properties (absorption properties) in their applications of paper diaper, sanitary napkin, etc., as well as absorbent materials and the absorbent product using such absorbent resins have been proposed.
  • absorbent resins, absorbent materials and absorbent products examples include: an absorbent resin disclosing a combination of a specific gel capacity, shear modulus and an extraction polymer content (US Patent No. 4,654,039); an absorbent resin having predeterined ranges of absorbying capacity and absorbency under pressure and gel stability, and a paper diaper and a sanitary napkin using such absorbent resin (Japanese Laid-Open Patent Publication No. 185550/1985 (Tokukaisho 60-185550)), (Japanese Laid-Open Patent Publication No. 185551/1985 (Tokukaisho 60-185551)) and (Japanese Laid-Open Patent Publication No.
  • an object of the present invention is to eliminate the above-mentioned problems and to provide an absorbing agent having excellent absorption properties such as very high liquid diffusivity and a stability over time of the absorbing capacity irrespectively of the structures of the resin concentration, the absorbent material, for example, when it is used as sanitary goods, etc., as well as a process of manufacturing such absorbing agent and the absorbent product including the absorbing agent
  • Another object of the present invention is to provide an absorbing agent having excellent properties, especially absorption properties in terms of maintaining very high liquid diffusivity and absorbing capacity even with high resin concentrations.
  • an absorbing agent is obtained by preparing an absorbing agent precursor by polymerisation of an unsaturated carboxylic acid monomer or a salt thereof and adjusting the particle diameter of the precursor to have an average particle diameter in the range 200 - 600 ⁇ m and including up to 10 percent by weight of particles having a particle diameter of less than 106 ⁇ m, and performing a heat treatment on said precursor in the presence of a surface crosslinking agent so that the absorbing agent has a diffusing absorbency under pressure of not less than 30 g/g after absorption has continued for 60 minutes, expressed as the weight of physiological saline absorbed per unit weight of absorbing agent under an applied load of 20 g/cm 2 .
  • the absorbing agent thus obtained by synthesizing the precursor of the absorbing agent and applying the heat treatment in a presence of a specific surface crosslinking agent, and absorbent materials and absorbent products including such absorbing agent, exhibit excellent performance such as very high liquid diffusivity, absorbing capacity, etc., even when the amount of use of the absorbent resin and the resin concentration are high.
  • the present invention provides an absorbent material comprising not less than 40% by weight of an absorbing agent (as hereinbefore described) and a hydrophilic fibre.
  • the present invention provides an absorbent product comprising an absorbent layer including an absorbent material (as hereinbefore described), the material having a water soluble content from above 0 up to 7% by weight, the absorbent layer being sandwiched between a sheet which is permeable to liquid and a sheet which is impermeable to liquid.
  • an absorbent product comprising an absorbent layer including an absorbent material (as hereinbefore described), the material having a water soluble content from above 0 up to 7% by weight, the absorbent layer being sandwiched between a sheet which is permeable to liquid and a sheet which is impermeable to liquid.
  • the diffusing absorbency under pressure in the present invention suggests a new property value for evaluating the absorbency under pressure of the absorbing agent and the absorbent material in view of the diffusivity of the aqueous liquid wherein the weighing capacity of the absorbent resin is high and resin particles are tightly linked one another by an external force.
  • the diffusing absorbency under pressure is computed based on values measured when a predetermined time elapsed after the absorption is started under predetermined conditions, for example, after 20 minutes, 30 minutes, and 60 minutes, etc.
  • the method of measuring the diffusing absorbency under pressure will be explained in below-mentioned embodiments.
  • the diffusing absorbency under pressure enables evaluations of new properties of the absorbing agent, the absorbent material, i.e., the absorbent resin. Namely, the diffusing absorbency under pressure evaluates the uniformity and the diffusivity of the absorbent resin in the aqueous liquid in a resin layer direction (hereinafter simply referred to as a lateral direction), or an actual absorbing capacity of the absorbent resin as a whole.
  • the liquid diffusivity in a lateral direction (liquid diffusivity and liquid transmissivity) is an important factor of absorbing a large amount of aqueous liquid.
  • the absorbing ability of the absorbent material mainly composed of the absorbing agent (absorbent resin) and hydrophilic fiber can be easily estimated especially in the absorbent resin in the absorbent material having high percent by weight (hereinafter referred to as a resin concentration) of the absorbent resin.
  • a resin concentration percent by weight
  • the water soluble content in the present invention suggests property values for evaluating the rediffusivity of the aqueous liquid after a long time elapsed when the absorbent resin has excellent diffusing absorbency under pressure and evaluating the ability of maintaining absorbed aqueous liquid for a long period of time.
  • the described water soluble content is measured under predetermined conditions. The method of measuring the water soluble content will be described in detail in the below-mentioned embodiments.
  • the absorbent resin has excellent diffusing absorbency under pressure, if the water soluble content thereof is outside the preferred range, the amount of wet back of the aqueous liquid after a long period of time elapsed tends to increase.
  • the absorbing agent having excellent properties such as very high liquid diffusivity and stable absorbing capacity for a long period of time without being much affected by the configuration of the resin concentration or the absorbent material, etc., the process of manufacturing thereof and the absorbent product including such absorbing agent will be explained.
  • the absorbing agent of the present invention has the diffusing absorbency under pressure of not less than 30 g/g.
  • the absorbent resin having the diffusing absorbency under pressure of less than 30 g/g i.e., the absorbent resin
  • the liquid diffusivity in the lateral direction in the absorbent material (high concentration) with an increased resin concentration is deteriorated, and the absorbing capacity of the absorbent material is lowered.
  • the diffusing absorbency under pressure is not less than 30 g/g, and most preferably not less than 32 g/g. If the water soluble content is above 7 percent by weight, the amount of wet back of the aqueous liquid after a long time elapsed will increase.
  • the water soluble content is not more than 5 percent by weight, and more preferably not more than 3 percent by weight.
  • the diffusing absorbency under pressure is determined by values measured when 60 minutes elapsed after the absorption is started under predetermined conditions.
  • the absorbing agent having the diffusing absorbency under pressure of not less than 15 g/g computed from the value measured when 20 minutes elapsed after the absorption is started is preferable, and those having the diffusing absorbency under pressure of not less than 20 g/g is more preferable.
  • the absorbent product of the present invention is characterized by including the absorbing material having the described excellent properties, such absorbent material including hydrophilic fiber.
  • the structures of the absorbent material including the absorbing agent and a hydrophilic fiber include: the structure wherein an absorbing agent and a hydrophilic fiber are uniformly mixed; a structure wherein the absorbing agent is sandwiched between layered hydrophilic fiber; a structure wherein the absorbing agent and the hydrophilic fiber are homogeneously mixed so as to form a layer and a hydrophilic fiber is formed thereon; the structure wherein the absorbing agent is sandwiched between the layered hydrophilic fiber and the layer formed of mixing uniformly the absorbing agent and the hydrophilic fiber.
  • the absorbent material is obtained by forming the absorbing agent in a sheet by mixing a predetermined amount of water with respect to the absorbing agent.
  • the structure of the absorbent material is not limited to the examplified structure.
  • hydrophilic fiber examples include: a cellulose fiber such as a mechanical pulp, a chemical pulp, a semichemical pulp, a dissolve pulp, etc.; an artificial cellulose fiber such as rayon, acetate, and the like. Among the above-listed fiber; cellulose fiber is preferable.
  • the hydrophilic fiber may include a synthetic fiber such as polyamide, polyester, polyolefin, etc.
  • the hydrophilic fiber of the present invention is not limited to the above-listed fibers.
  • the absorbing agent of the present invention is characterized in that that the ratio of the hydrophilic fiber in the absorbent material is above 0, and not more than 60 percent by weight, more preferably not less than 20 percent by weight and not more than 40 percent by weight.
  • the performances of the absorbent resin of the present invention can be fully exhibited irrespectively of the ratio of the hydrophilic fiber in the absorbent material. In addition, the performances of the absorbing agent are hardly affected by the described configuration of the absorbent material.
  • the absorbent material namely the hydrophilic fibers may be linked by using an adhesive binder.
  • the strength and the shape retention before and while using the absorbent material can be high.
  • Examples of such adhesive binder include: thermal fusing fiber such as polyethylene, polypropylene, ethylene-propylene copolymer, 1-butene-ethylene copolymer, and the like, emulsion having an adhesive property, etc. Only one kind of the above-listed adhesive binder may be adopted, or two or more kinds thereof may be suitably mixed and adopted.
  • the ratio by weight of the hydrophilic fiber to the adhesive binder is preferably in a range of 50/50 - 99/1, more preferably in a range of 70/30 - 95/5, still more preferably in a range of 80/20 - 95/5.
  • the absorbing agent in accordance with the present invention may be produced in the following manner.
  • a precursor of the absorbing agent is prepared by performing an aqueous solution polymerization of hydrophilic unsaturated monomer having at least 50 mole percent neutralized acrylic acid as a main component in a presence of the crosslinking agent and the dispersant using a certain amount of the crosslinking agent having a specific composition.
  • the precursor of the absorbing agent is adjusted so as to have a specific range of water content and a particle diameter of a specific range.
  • a heat treatment is applied to the precursor of the absorbing agent in the presence of the surface crosslinking agent.
  • the hydrophilic unsaturated monomer used as a raw material of the present invention includes acrylic acid and a neutralized material thereof as a main component.
  • acrylic acid and a neutralized material thereof as a main component.
  • the hydrophilic unsaturated monomer may include an unsaturated monomer other than acrylic acid.
  • unsaturated monomer other than acrylic acid is not especially limited.
  • such examples include: an anionic unsaturated monomer such as methacrylic acid, maleic acid, vinylsulfonic acid, styrenesulfonic acid, 2-(meth)acrylamide-2-metylpropanesulfonic acid, 2-(meth)acryloylethanesulfonic acid, 2-(meth)acryloylpropanesulfonic acid, etc., and salts thereof; a nonionic unsaturated monomer including hydrophilic groups such as acrylamide, methacrylamide, N-ethyl(meth)acrylamide, N-n-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hidroxylethyl (meth)acrylate, 2-hydroxylpropyl (meth)acrylate, meth
  • the above-mentioned additional hydrophilic unsaturated monomer is preferably used in an amount not more than 50 percent by weight with respect to the total amount of the acrylic acid and the neutralized product thereof used as a main component.
  • the crosslinking agent of the present invention is obtained by the esterification reaction of polyhydroxy alcohol having not more than six carbon atoms and at least three hydroxy groups (hereinafter referred to as a polyhydroxy alcohol) and an unsaturated carboxylic acid among unsaturated carboxylates such as acrylate having plural functional groups (hereinafter referred to as polyfunctional); or an transesterification of polyhydroxy alcohol having at least three hydroxy groups and a unsaturated carboxylic ester.
  • the unsaturated carboxylic ester wherein all the hydroxyl groups of polyhydroxy alcohol having at least three hydroxy groups and the unsaturated carboxylic acid are ester exchanged, i.e., a desired unsaturated carboxylic ester at high selectivity and high yield at low cost.
  • a desired unsaturated carboxylic ester at high selectivity and high yield at low cost.
  • a large amount of a high boiling-point compound having at least two polyhydroxy alcohol structures in a molecule is generated.
  • Inventors of the present invention made earnest researches to achieve the absorbent resin of improved performances prepared by performing an aqueous solution polymerization of hydrophilic unsaturated monomer using industrially available unsaturated carboxylic ester, i.e., unsaturated carboxylic ester including such high-boiling point compound as a crosslinking agent.
  • unsaturated carboxylic ester including such high-boiling point compound as a crosslinking agent.
  • the absorbent resin i.e., the absorbing agent
  • the absorbent resin which shows excellent properties including diffusing absorbency under pressure and liquid diffusivity, etc., and contains smaller amount of water soluble content.
  • the crosslinking agent adjusted so as to have a predetermined range of the high-boiling point component is used in a specific amount in the presence of the dispersant, the absorbing agent having a small amount of the water-soluble content and improved absorbency under pressure, etc., can be achieved.
  • the crosslinking agent of the present invention is composed of an ester compound of a polyhydroxy alcohol having not more than six carbon atoms and at least three hydroxy groups and an unsaturated carboxylic acid, wherein a ratio in molecular weight of the compound to a standard compound in which all the hydroxy groups in polyhydroxy alcohol having at least three hydroxy groups are ester-linked to the unsaturated carboxylic acid is in the range of from 0.7/1 to less than 1.3/1, and a high-boiling point having at least two alcohol structures, and a weight ratio of the main component of the crosslinking agent to the high boiling point in a range of 75/25 - 99/1.
  • the alcohol having at least three hydroxy groups used in preparing the crosslinking agent is not specified.
  • preferable examples of the alcohols include: glycerin, trimethylolethane, tetramethylolethane, trimethylolpropane, tetrahydroxyethane, pentaerythritol, etc.
  • trimethylolpropane is especially preferable.
  • unsaturated carboxylic acid used in the preparation of the crosslinking agent any of the previously listed hydrophilic unsaturated monomers having at least one carboxyl group may be used. However, acrylic acid is especially preferable.
  • the main component of the crosslinking agent may be a compound in which a ratio in molecular weight of the compound to a standard compound wherein all the hydroxyl groups of the polyhydroxy alcohol having at least three hydroxy groups are ester-linked to the unsaturated carboxylic acid among multifunctional unsaturated carboxylates which include polyhydroxy alcohol having at least three hydroxy groups as a alcohol component and an unsaturated carboxylic acid as an acid component is in a range between 0.7 to less than 1.3.
  • examples of the main component of the crosslinking agent include: trimethylolpropane triacrylate; trimethylolpropane diacrylate; trimethylolpropane diacrylatemono( ⁇ -acryloyloxypropionate), and the like.
  • examples of the main component of the crosslinking agent include: glycerintriacrylate, glycerinditriacrylate, etc.
  • examples of the main component of the crosslinking agent include: trimethylolethanetriacrylate, trimethilolethane diacrylate, and the like.
  • examples of the main component of the crosslinking agent include: tetramethylol ethane tetracrylate, tetramethylolethane triacrylate, etc.
  • examples of the main component of the present invention includes tetrahydroxyethane tetracrylate, tetrahydroxy ethane triacrrylate, and the like.
  • pentaerythritol is used as polyhydroxy alcohol having at least three hydroxy groups and acrylic acid as unsaturated carboxylic acid
  • penthaerythritol tetracrylate, pentaerythritol triacrylate, etc. may be used.
  • the high-boiling point compound included in the crosslinking agent having a complicated structure is a by-product generated when synthesizing the main component of the crosslinking agent.
  • examples of the high-boiling point component include: condensation products having at least two trimethylol propane structures in a molecule such as a compound generated from an additional reaction of trimethylolpropane triacrylate and trimethylolpropane diacrylate, a dimer of trimethylolpropane diacrylate, a compound generated by an additional reaction between trimethylolpropane diacrylate and trimethylolpropane monoacrylate, etc.
  • the weight ratio of the crosslinking agent main component and the high boiling point component in the crosslinking agent is in a range of 75/25 - 99/1, and preferably in a range of 80/20 - 90/10.
  • the weight ratio of the main component of the crosslinking agent to the high boiling point component in the crosslinking agent is less than 75/25, i.e., when the ratio of the main component of the crosslinking agent to the total amount of the crosslinking agent main component and the high boiling point component is less than 75 percent by weight (i.e., when the ratio of the high boiling point is above 25 percent by weight), even when the dispersant of the present invention is used, the absorbing agent which shows excellent diffusing absorbency under pressure and the liquid diffusivity and the absorbing agent having a smaller amount of water soluble content cannot be achieved.
  • the crosslinking agent in which the ratio in weight of the crosslinking agent main component and the high boiling component is above 99/1 i.e., the crosslinking agent in which the ratio of the main component with respect to the total amount of the main component of the crosslinking agent and the high boiling point component is above 99 percent by weight (i.e., the ratio of the high-boiling point component is less than 1 percent by weight) is not easily obtainable. Therefore, it is not industrially preferable.
  • the crosslinking agent having the main component ratio of the crosslinking agent of above 99 percent by weight compared to the case of using the crosslinking agent in an amount of 75 percent by weight to 99 percent by weight, significant effects cannot be achieved.
  • the amount of use of the crosslinking agent is not less than 0.05 mole percent and not more than 0.5 mole percent with respect to the hydrophilic unsaturated monomer, and it is preferably not less than 0.07 mole percent and not more than 0.2 mole percent.
  • the amount of use of the crosslinking agent is less than 0.05 mole percent or above 0.5 mole percent, the diffusing absorbency under pressure of the absorbing agent is lowered, and the amount of the water-soluble content increases. Therefore, it is industrially unpreferable.
  • the amount of use of the crosslinking agent should be calculated based on the compound wherein all the hydroxy groups of the polyhydroxy alcohol having at least three hydroxy groups are ester-linked to the unsaturated carboxylates, i.e, based on the molecular weight of the main component of the crosslinking agent.
  • the compound which is homogeneously dissolved in water and is compatible with the crosslinking agent is preferable, and in general, industrially obtainable compounds are preferable.
  • examples of such dispersant include: a nonionic surface active agent such as sorbitan aliphatic acid ester, polyoxyethylene sorbitan aliphatic ester, polyglycerin aliphatic ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene acyl ether, cane sugar aliphatic acid ester, and the like; an anionic surface active agent such as higher alcohol sulfate ester, alkyl naphthalene sulfonic acid salt, alkylpolyoxyethylene sulphate salt, dialkyl sulfosuccinate, and the like; a cationic surface active agent such as alkyl quaternary ammonium salts, alkyl amine salts, and
  • a water soluble surface active agent, and water diffusible surface active agent are preferable, and a nonionic surface active agent having at least 10 HLB (hydrophilic-lipophilic balance) is the most preferable.
  • the amount of use of the dispersant is preferably in the range of 1 - 100 percent by weight with respect to the crosslinking agent, more preferably in the range of 5 - 50 percent by weight.
  • the amount of use of the dispersant is preferably in the range of 0.005 - 0.5 parts by weight with respect to 100 parts by weight of the precursor of the absorbing agent resulting from the hydrophilic unsaturated monomer.
  • the method of mixing (adding) the dispersant in the aqueous solution polymerization is not especially limited.
  • the mixed solution may be mixed with the hydrophilic unsaturated monomer or aqueous solution thereof.
  • the hydrophilic unsaturated monomer or the solution thereof may be mixed.
  • the resulting mixed solution may be mixed with the rest of the hydrophilic unsaturated monomer and/or the solution.
  • the resulting solution may be mixed with the rest of the hydrophilic unsatuated monomer or the solution thereof.
  • the process wherein after mixing the crosslinking agent, the dispersant and a part of the hydrophilic unsaturated monomer or the solution thereof, the resulting mixed solution is mixed with the rest of hydrophilic unsaturated monomer or the solution thereof is preferable.
  • the process wherein after mixing the crosslinking agent, the dispersant, and a part of the acrylic acid as hydrophilic unsaturated monomer, or the solution thereof, the resulting mixed solution may be mixed with the rest of the hydrophilic unsaturated monomer or the solution thereof (neutralized polymer of acrylic acid) is more preferable.
  • the concentration of the hydrophilic unsaturated monomer in solution is preferably in the range between 25 percent by weight and a percent by weight of the saturated concentration, more preferably in the range between 30 percent by weight and 45 percent by weight.
  • a radical polymerization initiator such as potassium persulfate, ammonium persulfate, sodium persulfate, t-buthylhydroperoxide, hydrogen peroxide, 2,2'-azobis(2-amidinopropane)dihydrochloride, etc., or an active energy ray, such as an ultraviolet ray, or an electron ray, etc.
  • an oxidative radical polymerization initiator a redox polymerization may be carried out by simultaneously using a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, L-ascorbic acid, etc.
  • the amount of use of the polymerization initiator is preferably in the range of 0.001 - 2 mole percent, more preferably in the range of 0.01 - 0.5 mole percent.
  • the absorbing agent in accordance with the present invention is prepared by applying a heat treatment to the precursor of the absorbing agent obtained by the polymerization reaction in a solution so as to have a water content of less than 10 percent and the average particle diameter of 200 - 600 ⁇ m and a content of particles having a diameter of less than 106 ⁇ m of not more than 10 percent by weight in the presence of the surface crosslinking agent.
  • the resulting precursor of the absorbing agent may have, for example, undefined, globular (spherical), leaflet, granular shape, and the like.
  • the precursor of the absorbing agent may be a primary particle, or the granular of primary particle.
  • the absorbing agent having excellent dispersed absorbency under pressure, etc. cannot be achieved.
  • a known surface crosslinking agent is used, and a compound reactive to a carboxyl group is suitable.
  • Examples of such surface crosslinking agent include: polyhydroxy alcohol compounds having at least two hydroxy groups such as ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polypropylene glycol, glycerol, polyglycerol, 2-butene-1,4-diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,2-cyclohexanol, trimethylolpropane, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropy
  • the solubility parameter is a value normally used as a factor representing the polarity of the compound.
  • the solubility parameter ⁇ (J/m 3 ) 1/2 of the solvent described in pages 527-539 (polymer handbook, the third edition (Wiley Interscience Co., Ltd.)) is applied.
  • the solubility parameter of the solvent which is not described in the book, the value obtained by substituting the condensation energy constant of Hoy described on page 525 to the formula of Small described on page 524 of the book can be applied.
  • a compound reactive to a carboxylic group having a solubility parameter of more than 2.56 ⁇ 10 4 (J/m 3 ) 1/2 (12.5 (cal/cm 3 ) 1/2 ) is preferable, and a compound having a solubility parameter of more than 2.66 ⁇ 10 4 (J/m 3 ) 1/2 (13.0 (cal/cm 3 ) 1/2 ) is more preferable.
  • first crosslinking agent examples include: ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, ethylene carbonate (1,3-dioxorane-2-one), propylene carbonate (4-methyl-1, 3-dioxorane-2-one), etc.
  • first surface crosslinking agent is not limited to the above example. Only one kind of such first surface crosslinking agent may be used, or more than two kinds thereof may be used.
  • the second surface crosslinking agent is preferably a compound which is reactive to a carboxyl group, having a solubility parameter of less than 2.56 ⁇ 10 4 (J/m 3 ) 1/2 (12.5 (cal/cm 3 ) 1/2 ) and more preferably in the range of 1.94 ⁇ 10 4 - 3.52 ⁇ 10 4 (J/m 3 ) 1/2 (9.5 - 12.0 (cal/cm 3 ) 1/2 .)
  • Examples of the second surface crosslinking agent include: diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 2,5-hexanediol, trimethylolpropane, diethanolamine, triethanolamine, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylenediamine, diethylenetriamine, triethylene tetramine, 2,4-tolylene diisocyanate, hex
  • a compound of at least one kind selected from the group of the first surface crosslinking agent, and a compound of at least one kind selected from the group of the second surface crosslinking agent may be mixed and used.
  • Suitable amount of use of the surface crosslinking agent differs depending on a compound to be used, or a combination, etc.
  • the surface crosslinking agent is preferably used in an amount in the range of 0.001 - 10 parts by weight, and more preferably in the range of 0.01 - 5 parts by weight.
  • the first surface crosslinking agent and the second surface crosslinking agent are used in combination, with respect to 100 parts by weight of the solid portion of the precursor of the absorbing agent, the first surface crosslinking agent is used in a range of 0.01 - 5 parts by weight, and the second surface crosslinking agent is used in a range between 0.001 - 1 parts by weight.
  • the first surface crosslinking agent is used in an amount of 0.1 - 2 parts by weight
  • the second surface crosslinking agent is used in the range of 0.005 - 0.5 parts by weight.
  • the amount of use of water differs depending on the kinds, particle diameter, water content, etc., of the precursor of the absorbing agent. However, the amount of use of water is preferably above 0 and less than 20 parts by weight, more preferably in the range of 0.5 - 10 parts by weight, with respect to 100 parts by weight of the solid portion of the precursor of the absorbing agent.
  • a hydrophilic organic solvent may be used as a solvent if necessary.
  • hydrophilic organic solvent include: lower alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, etc.; ketone such as acetone, etc.; ether such as dioxane, tetrahydrofrane, etc.; amide such as N,N-dimethyl formamid, etc., sulfoxide such as dimethylsulfoxide, etc.
  • Suitable amount of use of the hydrophilic organic solvent varies depending on kinds, particle diameter and water content of the precursor of the absorbing agent.
  • the content of the hydrophilic organic solvent is preferably not more than 20 parts by weight, more preferably in a range of from 0.1 - 10 parts by weight of 100 parts of the solid portion of the precursor of the absorbing agent.
  • the surface crosslinking agent when mixing the precursor of the absorbing agent with the surface crosslinking agent, for example, after dispersing the precursor of the absorbing agent in the hydrophilic organic solvent, the surface crosslinking agent may be mixed.
  • the mixing method is not especially limited. Among various mixing processes, the process wherein the surface crosslinking agent which is dissolved in water and/or hydrophilic organic solvent, when an occasion demands, is mixed with the precursor of the absorbing agent directly or by spraying or dropping it is preferable. When mixing with water, fine particles undissolvable in water or the surface active agent, etc., may be used in combination.
  • the mixer for use in mixing the precursor of the absorbing agent with the surface crosslinking agent preferably has a strong mixing force so that both can be mixed homogeneously and surely.
  • Examples of such mixer include: a cylindrical mixer, a double wall conical mixer, V-shaped mixer, ribbon type mixer, screw-type mixer, flow-type oven rotary desk mixer, air-flow type mixer, two-arm type kneader, internal mixer, grinding kneader, rotary mixer, screw type extruder, etc.
  • a heat treatment is applied so as to crosslink around the surface of the precursor of the absorbing agent.
  • Suitable temperature of applying the heat treatment varies depending on the surface crosslinking agent to be used. However, it is preferably in the range between 80 °C and 250 °C, more preferably in the range between 120 °C and 230 °C.
  • the heat treatment is suitably applied at temperature not less than 160 °C.
  • the heat treatment is applied at temperature below 80 °C (below 160 °C when using both the first and second surface crosslinking agents), a uniform crosslinking structure is not formed.
  • the absorbent resin having excellent properties such as diffusing absorbency under pressure, etc. cannot be obtained. Therefore, such condition is unpreferable. Besides, as it takes a long time for applying the heat treatment, the productivity is low. On the other hand, when the heat treatment is applied at above 250 °C, properties of the precursor of the absorbing agent are lowered, which results in poor performances of the absorbing agent. Thus, such condition is unpreferable.
  • the described heat treatment may be applied using general dryer, heating oven, etc.
  • dryer examples include: groove type mixing dryer, rotary dryer, desk dryer, fluidized layer dryer, air-flow type dryer, infrared radiation dryer, etc.
  • the absorbing agent resulting from the described manufacturing process has the diffusing absorbency under pressure of above 25 g/g when 60 minutes elapsed after the absorption started, and the water soluble content in the range between 0 percent by weight and 7 percent by weight. Therefore, the absorbing agent has described excellent absorbing properties.
  • the reason why the absorbing agent of the present invention shows excellent performances in its diffusing absorbency under pressure, etc., is not specified.
  • the dispersant as well as a specific amount of the crosslinking agent prepared so as to have a specific range of high-boiling point component
  • the high-boiling point component is homogeneously dispersed in the reaction system, and the crosslinking ability of the main component thereof disturbed by the high-boiling point component can be fully exhibited.
  • the crosslinking reaction by the high-boiling point component can be performed effectively.
  • the content of the water-soluble component can be significantly reduced.
  • the described absorbing agent is provided with excellent absorbing properties. Therefore, in the case of applying the absorbing agent to an absorbent material, for example, sanitary goods such as a paper diaper, sanitary napkin, incontinence pad, etc., even when the resin concentration in the absorbent material is high, such excellent properties that high diffusing absorbency under pressure, and low water soluble content can be obtained irrespectively of the structure of the absrobent material.
  • sanitary goods has small amount of wet back after a long period of time, very high liquid diffusivity, and a stabiity of keeping the amount of water for a long period of time, thereby providing the absorbent product which show excellent performances.
  • Such absorbing agent can be suitably used, especially in sanitary goods, such as paper diaper, sanitary napkin, a so-called incontinence pad, and the like, to meet the demand of higher performances and thinner type thereof.
  • sanitary goods such as paper diaper, sanitary napkin, a so-called incontinence pad, and the like.
  • the described process enalbes the absorbing agent which show excellent properties to be manufactured.
  • deodorant perfume, inorganic powder, foaming agent, pigment, dye, hydrophilic short fiber, synthetic fiber, fertilizer, oxidizing agent, reducing agent, water, salts, etc.
  • deodorant perfume, inorganic powder, foaming agent, pigment, dye, hydrophilic short fiber, synthetic fiber, fertilizer, oxidizing agent, reducing agent, water, salts, etc.
  • the absorbing agent, the absorbent material and the absorbent product which show excellent properties (absorbing properties) such as high liquid diffusivity and water absorbency under pressure, etc., even if the resin concentration is raised will be explained.
  • the absorbent material of the present invention includes at least 40 percent by weight of the absorbing agent having the diffusing absorbency under pressure of at least 30 g/g when 60 minutes elapsed after the absorption is started, preferably 50 percent by weight, more preferably 60 percent by weight, and most preferably 70 percent by weight.
  • the absorbing agent having the diffusing absorbency under pressure of at least 30 g/g measured when 60 minutes elapsed after the absorption is started is unpreferable because the liquid diffusivity in the lateral direction in the absorbent material (high concentration) having an increased resin concentration is lowered, and the absorbing capacity of the absorbent material becomes small.
  • the absorbing agent having the diffusing absorbency under pressure of not less than 30 g/g in addition to the diffusing absorbency under pressure, when 60 minutes elapsed after the absorption is started, it is preferable to include the absorbing agent having the diffusing absorbency under pressure of 15 g/g computed based on the value measured when 30 minutes elapsed after the absorption is started. Furthermore, it is most preferable to include the absorbing agent having the diffusing absorbency under pressure of at least 15 g/g computed based on the value measured when 20 minutes elapsed after the absorption is started.
  • the absorbing agent of the present invention has the diffusing absorbency under pressure of not less than 15 g/g when 30 minutes elapsed after the absorption is started and the diffusing absorbency under pressure of not less than 30 g/g when 60 minutes elapsed. It is more preferable that the diffusing absorbency under pressure is not less than 15 g/g when 20 minutes elapsed after the absorption is started, and the diffusing absorbency under pressure measured when 60 minutes elapsed after the absorption is started is not less than 30 g/g.
  • the absorbing agent has the diffusing absorbency under pressure of less than 15 g/g when 30 minutes elapsed after the absorption is started is unpreferable because the liquid diffusivility in lateral direction would be deteriorated, and the absorbing force of the absorbent material is lowered.
  • the absorbent material in accordance with the present invention includes the hydrophilic fiber.
  • the structure of the absorbent material may be the aforementioned structure, but not especially limited. However, it is preferable that the absorbing agent and the hydrophilic fiber are homogeneously mixed so as to have the ratio of the absorbing agent in the absorbent material is not less than 40 percent by weight. It is still more preferable that the absorbing agent and the hydrophilic fiber are uniformly mixed so as to have the absorbing agent used in an amount not less than 50 percent by weight, preferably 60 percent by weight, more preferably 70 percent by weight with respect to the total amount of the absorbing agent and the hydrophilic agent.
  • the absorbent material can fully exhibit the absorbing properties.
  • the higher is the resin concentration in the absorbent material the more obvious are the properties of the absorbing agent and the absorbent material of the present invention.
  • absorbent materials i.e., hydrophilic fibers may be linked one another using the described adhesive binder.
  • the absorbing agent of the present invention may also be obtained by first synthesizing the precursor of the absorbing agent and then applying the heat treatment to the precursor of the absorbing agent in a presence of a specific surface crosslinking agent.
  • the precursor of the absorbing agent has an average particle diameter in the range of 200 - 600 ⁇ m, and includes 10 percent by weight of particles having a particle diameter of 106 ⁇ m.
  • Such precursor of the absorbing agent is a resin of forming hydrogel by absorbing a large amount of water.
  • the precursor of the absorbing agent is synthesized by the aqueous solution polymerization.
  • Examples of the precursor of the absorbing agent include: a partially neutralized crosslinked polymer of polyacrylic acid, a hydrolyzed graft polymer of starch-acrylonitrile, a neutralized graft polymer of starch-acrylic acid, a saponified copolymer of vinyl acetateacrylic ester, a hydrolyzed copolymer of acrylonitrile or of acrylamide, or a crosslinkied polymer thereof, crosslinked denatured polyvinyl alcohol containing carboxyl group, a copolymer of crosslinked isobuthylene-maleic anhydride, and the like.
  • the precursor of the absorbing agent may be obtained by performing a polymerization or a copolymerization of at least kind selected from unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, ⁇ -acryloxypropionic acid or the above acids in a neutralized form, and further pulverizing or clssifing the polymer, if necessary, to have the above-defined particle diameter.
  • unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, ⁇ -acryloxypropionic acid or the above acids in a neutralized form
  • unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, ⁇ -acryloxypropionic acid or the above acids in a neutral
  • the precursor of the absorbing agent may be a copolymer of the monomer and the other monomer which is copolymerisible with the monomer.
  • the other monomer include: the exemplified unsaturated monomer, i.e., the anionic unsaturated monomer and salts thereof; a nonionic unsaturated monomer having a hydrophilic group; a cationic unsaturated monomer, etc.
  • the precursor of the absorbing agent includes a carboxyl group.
  • the amount of the included carboxyl group in the precursor is not especially limited. However, it is preferable that the carboxyl group of not less than 0.01 equivalent value exits with respect to 100 g of the precursor of the absorbing agent.
  • the precursor of the absorbing agent is, for example, a crosslinked polymer of partially neutralized polyacrylic acid, it is preferable that the ratio of unneutralized polyacrylic acid in the crosslinked compound is in the range of 1 - 60 mole percent, more preferably 10 - 50 mole percent.
  • the inside of the precursor of the absorbing agent is crosslinked by reacting or copolymerizing with the crosslinking agent including plural polymerizable unsaturated groups and plural reactive groups.
  • the precursor of the absorbing agent may be the self crosslinkable type which does not require the crosslinking agent.
  • crosslinking agent examples include: N,N'-methylenebis(meth)acrylamide, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, glycerin acrylate methacrylate, ethylene oxide denatured trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallylphosphate, triallylamine, poly(meth)aryloxyalkane, (poly)ethylene glycol diglycydil ether, glycerol diglycydil ether, ethylene glycol, polyethylene glycol, propy
  • the above-listed crosslinking agent Only one kind of the above-listed crosslinking agent may be adopted, or two or more kinds thereof may be suitably mixed and adopted.
  • the above-listed compounds it is preferable to use the compound including plural polymerizable unsaturated group as a crosslinking agent.
  • the crosslinking agent is used in an amount in the range of 0.005 - 2 mole percent, more preferably in the range of 0.05 - 1 mole percent. If the amount of use of the crosslinking agent is less than 0.005 mole percent or more than 2 mole percent, the diffusing absorbency under pressure of the absorbing agent will be lowered. Thus, such condition is unpreferable.
  • the above-exemplified radical polymerization initiator or the active energy ray, etc., may be used.
  • the described precursor of the absorbing agent does not have the diffusing absorbency under pressure in the preferable range of the present invention. Therefore, it is required to set the crosslinked density in a vicinity of the surface of the precursor of the absorbing agent higher than the inside thereof by adopting the surface crosslinking agent. Namely, by crosslinking around the surface of the precursor of the absorbing agent using a specific surface crosslinking agent, the absorbing agent of the present invention can be achieved.
  • the absorbing agent in accordance with the present invention is prepared by adjusting the precursor of the absorbing agent obtained by the aqueous solution polymerization so as to have an average particle diameter of 200- 600 ⁇ m, and not more than 10 percent by weight of the particle diameter below 106 ⁇ m by classification, etc., and thereafter applying a heat treatment to the precursor of the absorbing agent in the presence of the specific surface crosslinking agent.
  • the precursor of the absorbing agent may be formed in granules of the defined shape or in the shape of undefined, globular, leaflet, glanular, etc.
  • the precursor of the absorbing agent may be a primary particle, or the granular of primary particle.
  • the average particle diameter is outside the range of 200 - 600 ⁇ m, and the case where the ratio of the particles having a diameter of 106 ⁇ m is above 10 percent by weight, absorbing agents having excellent properties such as diffusing absorbency under pressure, etc., cannot be obtained.
  • the surface crosslinking agent is a combination of the first surface crosslinking agent and the second crosslinking agent having mutually different solubility parameters (SP value).
  • SP value solubility parameters
  • a compound of at least one kind selecting from the group of the first surface crosslinking agent and the compound of at least one kind selecting from the group of the second surface crosslinking agent are mixed and used.
  • the previously described amount of use for the amount of use of the surface crosslinking agent, and the method of mixing the precursor of the absorbing agent with the surface crosslinking agent, the previously described amount of use, the mixing method, the mixer, etc., may be used.
  • the previously described solvent water and/or hydrophilic organic solvent
  • Suitable temperature of applying the heat treatment varies depending on the surface crosslinking agent. However, it is preferably in the range of 160 °C to 250 °C.
  • the heat treatment is applied at temperature below 160 °C, a homogeneous crosslinking structure may not be formed, and the absorbing agent having excellent performances in its diffusing absorbency under pressure, etc., cannot be obtained. Therefore, such condition is unpreferable.
  • a productivity would be lowered.
  • the heat treatment at temperature above 250 °C as the properties of the precursor of the absorbing agent are lowered, and the performances of the absorbing agent would be poor. Therefore, such condition is also unpreferable.
  • the described heat treatment is performed using the examplified dryer or a heat oven.
  • the absorbing agent resulting from the described process has 15 g/g of the diffusing absorbency under pressure measured when 30 minutes elapsed after the absorption is started, and the diffusing absorbency under pressure of 30 g/g after 60 minutes elapsed.
  • the absorbent material contains such absorbing agent in an amount of not less than 40 percent by weight. Therefore, the absorbing agent and the absorbent material show described excellent absorbing properties. Therefore, for example, in the case where it is used in the absorbent product, the absorbent material can provide the excellent properties such as high liquid diffusivity, water retaining property, etc., even in the case of using a large amount of absorbing agent or using the absorbent material having high resin concentration.
  • the absorbent product in accordance with the present invention includes an absorbing layer including the absorbent material having the described structure which is sandwiched between a liquid permeable sheet and an impermeable sheet. Since the absorbent product is provided with the absorbing layer including the absorbent material having the described arrangement, the above-mentioned excellent water absorbing properties can be achieved. Examples of the absorbent product include: sanitary goods such as paper diaper, sanitary napkin, incontinence pad, etc. However, the present invention is not limited to the above-listed absorbent products. Since the absorbent product of the present invention has excellent absorbing properties, in its application of paper diaper, etc., the leakage of urea can be prevented, and thus the paper diaper can be maintained dry.
  • a sheet which is permeabile to liquid (hereinafter referred to as a liquid permeable sheet) is composed of a material which is transmissive to aqueous liquid.
  • a material which is transmissive to aqueous liquid for the material of the liquid permeable sheet, nonwoven fabric, woven fabric; a porous synthetic resin film such as polyethylene, polypropylene, polyester, polyamide, etc., may be used.
  • the sheet which is impermeabile to liquid (hereinafter referred to as liquid impermeable sheet) is made of a material having properties that aqueous liquid is not transmitted.
  • a synthetic resin film such as polyethylene, polypropylene, ethylenevinylacetate, polyvinyl chloride; a film composed of the above-mentioned synthetic resin and nonwoven fabric, a film composed of the synthetic material of synthetic resin and woven fabric, etc.
  • a liquid impermeable sheet may have property of transmitting vapor.
  • the arrangement of the absorbing layer is not particularly limited, as long as the described absorbent material is included.
  • the method of manufacturaing the absorbing layer is not especially limited.
  • the method of sandwitching the absorbing layer between the liquid permeable sheet and the liquid impermeable sheet, and the method of manufacturing the absorbnet product are not especially limited.
  • deodorant perfume, inorganic powder, foaming agent, pigment, dye, hydrophilic short fiber, synthetic fiber, fertilizer, oxidizing agent, reducing agent, water, salts, etc.
  • deodorant, perfume, inorganic powder, foaming agent, pigment, dye, hydrophilic short fiber, synthetic fiber, fertilizer, oxidizing agent, reducing agent, water, salts, etc. may be added to the resulting absorbing agent, absrobent material or absorbent product prepared by the process of the present invention, which enables them to have various functions.
  • 0.2 grams of the absorbing agent (precursor of the absorbing agent) was uniformly placed into a bag like a tea-bag (40 mm ⁇ 150 mm) made of nonwoven fabric, and was immersed into a solution of 0.9 percent by weight of sodium chloride (physiological saline solution). After leaving it for 60 minutes, the bag was taken out. Then, the bag was subjected to hydro-extraction for a predetermined period of time, and the weight W 1a (g) of the bag was measured. Further, the same processes are carried out without using the absorbing agent, and the weight W 0a (g) of the bag was measured.
  • 0.2 grams of the absorbing agent was uniformly placed into a bag (60 mm ⁇ 60 mm) made of nonwoven fabric, and was immersed into a solution of sodium chloride of 0.9 percent by weight (physiological saline solution). After leaving it for 60 minutes, the bag was taken out. Then, the bag was subjected to hydro-extraction for 3 minutes at 250 G using a centrifugal separator, the weight W 1b (g) of the bag was measured. Further, the same processes are carried out without using the absorbent resins, and the weight W 0b (g) of the bag was measured.
  • the measuring device includes a balance 1, a container 2 placed on the balance 1 of a predetermined capacity, an air-intake pipe 3, a conduit 4, a glass filter 6, and a measuring section 5 that is placed on the glass filter 6.
  • the container 2 has an opening 2a on its top portion and an opening 2b on its side portion, and the air-intake pipe 3 is inserted through the opening 2a while the conduit 4 is fixed to the opening 2b.
  • a predetermined amount of physiological saline solution 12 is placed in the container 2.
  • the lower end portion of the air-intake pipe 3 is dipped into the physiological saline solution 12.
  • the glass filter 6 has a diameter of 70 mm.
  • the container 2 and the glass filter 6 are connected to each other through the conduit 4.
  • the glass filter 6 is fixed at a position slightly above the lower end of the air-intake pipe 3.
  • the measuring section 5 is provided with a paper filter 7, a sheet 8, a supporting cylinder 9, a metal gauze 10 that is affixed to the bottom of the supporting cylinder 9, and a weight 11.
  • the paper filter 7, the sheet 8, and the supporting cylinder 9 that is, the metal gauze 10) are placed on the glass filter 6 in this order, and the weight 11 is placed on the metal gauze 10 inside the supporting cylinder 9.
  • the sheet 8 is made of polyethylene terephthalate (PET) and is formed in a doughnut shape with a thickness of 0.1 mm having an opening at a center with a diameter of 18 mm.
  • the supporting cylinder 9 has an inner diameter of 60 mm.
  • the metal gauze 10, made of stainless steel, is designed to be 400-mesh (the size of each mesh: 38 ⁇ m). Thus, a predetermined amount of the absorbing agent is uniformly scattered on the metal gauze 10.
  • the weight 11 is adjusted so that it can uniformly apply a load of 20 g/cm 2 to the metal gauze 10, that is, to the absorbing agent.
  • the diffusing absorbency under pressure of the absorbing agent was measured by using the measuring device having the above-mentioned arrangement. The following description will discuss the measuring method.
  • predetermined preparatory operations were carried out, such as a predetermined amount of physiological saline solution 12 was put into the container 2; the air-intake pipe 3 was inserted into the container 2; and other preparatory operations were performed.
  • the paper filter 7 was placed onto the glass filter 6.
  • the sheet 8 was placed on the paper filter 7 in such a manner that its opening was positioned at the center of the glass filter 6.
  • 1.5 g of the absorbent resins preferably, the absorbent resin 1.5 g prepared so as to have a particle diameter of 300 - 500 ⁇ m by classification, etc.
  • the metal gauze 10 that is, the supporting cylinder 9 whereon the absorbing agent and the weight 11 were placed, was placed on the sheet 8, in such a manner that the center of the supporting sylinder 9 coincides with the center of the glass filter 6.
  • the weight W 2 (g) of the physiological saline solution 12, which had been absorbed by the absorbing agent for 20, 30 or 60 minutes from the time when the supporting cylinder 9 was placed on the sheet 8 was measured by the balance 1. Further, as shown in Fig. 3, after passing through the opening of the sheet 8, the physiological saline solution 12 was absorbed by the absorbing agent while being uniformly diffused in a lateral direction.
  • the measuring device includes a bulet 21, a measuring plate 22, a conduit 23, a glass filter 24 placed on the measuring plate 22, and a measuring section 25 placed on the glass filter 24.
  • the bulet 21 is formed in substantialy T-shape and includes a main conduit 21a and side conduits 21b.
  • the main conduit 21a has an opening 21c on its top portion and an opening 21d at its bottom portion, and a stopcock 26 is fitted to the opening 21c, while the conduit 23 is mounted to the opening 21d.
  • the side conduit 21b is projected at a center on the side face of the main conduit 21a, and the leading end thereof has an opening in an upward direction.
  • the measuring plate 22 has an upper surface with a diameter of 70 mm.
  • the bulet 21 and the measuring plate 22 are completely through by the conduit 23.
  • the measuring plate 22, and the conduit 23, i.e., a continuos portion a predetermined amount of artificial urea 20 is placed.
  • the main conduit 21a of the bulet 21 has a scale.
  • the position of the liquid face 20a in the side conduit 21b has a predetermined height position below the liquid face 20b of the main conduit 21a.
  • the measuring section 25 includes a filter paper 27, a supporting cylinder 28, a nonwoven fabric 29 laminated on the bottom portion of the supporting cylinder 28 and a weight 30.
  • the measuring section 25 is arranged such that the filter paper 27, and the supporting cylinder 28 (nonwoven fabric 29) are placed in this order on the glass filter 24, and the weight 30 is placed in the supporting cylinder 28, i.e., on the nonwoven fabric 29.
  • the glass filter 24 is formed so as to have a diameter of 70 mm.
  • the supporting cylinder 28 has an inner diameter of 55 mm.
  • the absorbency under pressure of the absorbing agent was measured in the following manner.
  • a predetermined amount of artificial urea 20 (composition: 1.9 percent by weight of urea, 0.8 percent by weight of NaCl, 0.1 percent by weight of CaCl 2 , and 0.1 percent by weight of MgSO 4 ) was prepared, and was pured in the above-mentioned connected portion. Then, the opening 21c of the bulet 21 was closed with the stopcock 26, and a predetermined preparatory operation was performed such as placing the measuring plate 22 at a predetermined height position. Then, the filter paper 27 was placed on the glass filter 24 provided at the central portion of the measuring device 22. In the meantime, 0.20 g of the absorbing agent was uniformly diffused in the inside of the supporting cylinder 28, i.e., on the nonwoven fabric 29, and the weight 30 was placed on the absorbing agent.
  • the nonwoven fabric 29, i.e., the supporting cylinder 28 for storing therein the absorbing agent and the weight 30 was placed in such a manner that the center thereof coincided with the center of the glass filter 24.
  • the device of measuring the diffusing absorbency under pressure of the absorbent product (or absorbent material, for convenience, both absorbent material and the absorbent product are simply referred to as an absorbent product) will be briefly explained in referecne to Fig. 5 and Fig. 6.
  • members having the same functions as the aforementioned device used in measuring the diffusing absorbency under pressure will be designated by the same reference numerals, and thus the descriptions thereof shall be omitted here.
  • the measuring device includes: a balance 1, a container 2, an air-intake pipe 3, a conduit 4, and a glass filter 6 having a diameter of 120 mm, and a measuring section 15 placed on the glass filter 6.
  • the measuring section 15 includes a filter paper 7, a sheet 8, an angular supporting cylinder 19 and a weight 11. The described metal gauze is not provided.
  • the measuring section 15 includes the filter paper 7, the sheet 8 and the angular supporting cylinder 19 which are placed on the glass filter 6 in this order and the weight 11 placed in the inside of the angular supporting cylinder 19.
  • the sheet 8 is made of polyethylene terephthalate, and is formed in a reculangular shape with an opening with a size of 12.5 mm ⁇ 100 mm at the center and a thickness of 0.1 mm.
  • the angular supporting cylinder 19 is formed so as to have an inner size of 100 mm ⁇ 100 mm. Further, a predetermined size of the absorbent product is placed in the side of the anglular supporting cylinder 19.
  • Other arrangements of the measuring device is the same as the aforementioned measuring device for use in measuring the diffusing absorbency under pressure.
  • the diffusing absorbency under pressure of the absorbent product was measured using the measuring device having the described arrangement in the following manner.
  • the absorbent product is formed with a size of 100 mm ⁇ 100 mm. Then, predetermined preparatory operations were performed. Then, the filter paper 7 was placed on the glass filter 6, and the sheet 8 was placed on the filter sheet 7 in such a manner that its opening coincided with the center of the glass filter 6. Then, the angular supporting cylinder 19 was placed on the sheet 8 such that the central portion thereof coincided with the central portion of the glass filter 6.
  • the absorbent product was placed in the inside of the angular supporting cylinder 19, i.e., on the sheet 8, and the weight 11 was placed on the absorbent product.
  • the placement operations of the absorbent product and the weight 11 were quickly performed.
  • a weight W 3 (g) of physiological saline solution 12 absorbed by the absorbent product was measured over 30 minuates or 60 minutes.
  • the physiological saline solution 12 was absorbed by the absorbent product while the physiological saline solution 12 was being uniformly dispersed in the absorbent product in a lateral direction.
  • crosslinking agents used in Examples 1-6 and comparative examples 1-3 were prepared in the following manner.
  • an one-litter flask with four openings provided with an agitator, a water-separator with a cooling tube, a thermometer and an air-introducing tube 134 g of trimethylolpropane, 238 g of acrylic acid, 170 g of toluene, 24 g of p-toluenesulfonic acid and 0.6 g of hydroquinone were fed, and the flask was heated to 130 °C while introducing air thereinto.
  • Produced water was distilled off from a reaction system by an azeotropic dehydration with toluene, while a reaction was performed for a predetermined time.
  • reaction solution was transferred to a separating funnel, and after neutralizing the unreacted acrylic acid with 500 g of 10 percent by weight of NaOH aqueous solution and 300 g of 5 percent by weight of NaOH aqueous solution, the reaction solution was layered and washed with water (500 g each) several times until the washed liquid was neutralized. Then, to an organic layer, 0.06 g of hydroquinone monomethyl ether was added, and the toluene was distilled under reduced pressure, thereby obtaining a reaction product.
  • the reaction product was analyzed using the gas chromatography (GC), and the gel permeation chromatography (GPC).
  • GC gas chromatography
  • GPC gel permeation chromatography
  • the ratio of essential components of the cross-linking agent including trimethylolpropane triacrylate, trimethylolpropane diacrylate and trimethylolpropane diacrylatemono( ⁇ -acryloyloxypropionate) to a high boiling-point compound including a compound having at least two trimethylolpropane structures was 84/16.
  • reaction time was set longer than preparation 1, and a cross-linking agent B having a ratio by weight of a cross-linking main component to a high-boiling point component of 78/22 was obtained.
  • reaction time was set shorter than preparation 1, and a cross-linking agent C having a ratio by weight of a cross-linking main component to a high-boiling point component of 89/11 was obtained.
  • the same reaction as preparation 2 was performed in the same manner except that the reaction time was set still longer than preparation 2, and a comparative cross-linking agent having a ratio by weight of a comparative cross-linking main component to a high-boiling point component of 72/28 was obtained.
  • the resulting finely divided water-containing gel-like polymer was placed on a wire netting of 50 mesh and dried under hot air at 150 °C for 90 minutes. Then, the resulting dried polymer was pulverized by a vibrating mill and further classified by a wire netting of 20 mesh. As a result, an absorbent resin of undefined shape with a water content of 4 percent, an average particle diameter of 350 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 3 percent by weight was obtained. Namely, a precursor of the absorbing agent was obtained.
  • the absorbency under pressure by tea bag method and the water soluble content of the resulting precursor of the absorbing agent (hereinafter simply referred to as results) are shown in Table 1.
  • Example 1 The same reaction as Example 1 was performed in the same manner except that 4.8 g of the crosslinking agent B was used in replace of the crosslinking agent A used in Example 1. As a result, an absorbent resin of undefined shape with a water content of 5 percent, an average particle diameter of 300 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 6 percent by weight was obtained. Namely, a precursor of the absorbing agent was obtained.
  • Table 1 The results of this example are shown in Table 1.
  • Example 1 The same reaction as Example 1 was performed in the same manner except that 4.8 g of the crosslinking agent C was used in replace of the crosslinking agent A used in Example 1. As a result, an absorbent resin of undefined shape with a water content of 8 percent, an average particle diameter of 480 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 0.5 percent by weight was obtained. Namely, a precursor of the absorbing agent was obtained. The results of this example are shown in Table 1.
  • Example 1 The same reaction as Example 1 was performed in the same manner except that the amount of use of the crosslinking agent A was changed from 4.8 g to 6.8 g. As a result, an absorbent resin of undefined shape with a water content of 5 percent, an average particle diameter of 380 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 2 percent by weight was obtained. Namely, a precursor of the absorbing agent was obtained.
  • Table 1 The results of this example are shown in Table 1.
  • Example 1 The same reaction as Example 1 was performed in the same manner except that the amount of use the crosslinking agent A was changed from 4.8 g to 13.6 g. As a result, an absorbent resin of undefined shape with a water content of 4 percent, an average particle diameter of 400 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 1 percent by weight was obtained. Namely, a precursor of the absorbing agent was obtained.
  • Table 1 The results of this example are shown in Table 1.
  • Example 1 The same reaction as Example 1 was performed in the same manner except that 4.8 g of comparative crosslinking agent was used in replace of the crosslinking agent A used in Example 1. As a result, a comparative absorbent resin of undefined shape with a water content of 5 percent, an average particle diameter of 340 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 5 percent by weight was obtained. Namely, a precursor of the comparative absorbing agent was obtained. The results of this example are shown in Table 1.
  • Example 1 The same reaction as Example 1 was performed in the same manner except that polyoxyethylenesorbitan monostearate used in Example 1 was not used. As a result, a comparative absorbent resin of undefined shape with a water content of 4 percent, an average particle diameter of 370 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 3 percent by weight was obtained. Namely, a precursor of the comparative absorbing agent was obtained.
  • Table 1 The results of this example are shown in Table 1.
  • Example 1 The same reaction as Example 1 was performed in the same manner except that the amount of use the crosslinking agent A was changed from 4.8 g to 2.0 g. As a result, an absorbent resin of undefined shape with a water content of 5 percent, an average particle diameter of 390 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 2 percent by weight was obtained. Namely, a precursor of the absorbing agent was obtained.
  • Table 1 Absorbency by tea bag method (g/g) Water soluble Content (% by weight) Example 1 43 6 Example 2 44 7 Example 3 43 6 Example 4 40 4 Example 5 38 3 Example 6 40 5 Comparative Example 1 44 8 Comparative Example 2 44 8 Comparative Example 3 52 14
  • the absorbency by the tea bag method, the water soluble content, the diffusing absorbency under pressure and the absorbency under pressure of the absorbing agent (hereinafter simply referred to as results) are shown in Table 2.
  • Example 7 The same heat treatment as Example 7 was performed in the same manner except that 100 parts by weight of the precursor of the absorbing agents resulting from Examples 4 and 5 were used, and respective absorbing agents were obtained. The results of these examples are shown in Table 2.
  • Example 7 The same heating process as Example 7 was performed in the same manner except that 100 parts by weight of the precursor of the comparative absorbing agents resulting from Comparative Examples 1 and 3 were used, and respective comparative absorbing agents were obtained. The results of these examples are shown in Table 2.
  • a graft polymer of partially neutralized and crosslinked starch-acrylate (Sunwet IM3900P available from Hoechst Celanese Co., Ltd.) was used as a comparative absorbing agent.
  • the results of this comparative example are shown in Table 2.
  • a polymer of partially neutralized and crosslinked acrylate (Daiyawet US2-45Z; available from Mitsubishi Petrochemical Co., Ltd.) was used as a comparative absorbing agent.
  • the results of this comparative example are shown in Table 2.
  • a polymer of partially neutralized and crosslinked acrylate (Aquakeep SA-60; available from Sumitomo Seika Co., Ltd.) was used as a comparative absorbing agent.
  • the results of this comparative example are shown in Table 2.
  • An absorbent material was prepared in the same manner as Example 10 except that absorbing agents obtained from Examples 8 and 9 were used in replace of the absorbing agent used in Example 10, and respective absorbent products were obtained. The results are shown in Table 3.
  • the absorbent product was put on a so-called Cupy doll (height: 55 cm; and weight: 5 kg), and the doll was placed facing down. Thereafter, a tube was inserted between the absorbent product and the doll, and onto the position corresponding to the portion from which urea was to be discharged, 50 ml of physiological saline solution was poured each time, and a total amount of 250 ml of physiological saline solution was poured with an interval of 20 minutes. Then, after leaving the doll for 16 hours at 37 °C, the absorbent product was taken out.
  • An absorbent product was prepared in the same manner as Example 13 except that absorbent agents obtained from Examples 8 and 9 were used in replace of the absorbing agent used in Example 13.
  • the obtained amount (g) of the physiological saline solution from the absorbent product was measured. The results of these examples are shown in Table 4.
  • the absorbing agent of the present invention has high diffusing absorbency under pressure and low water soluble content.
  • the absorbent product prepared using an absorbent material having high resin concentration has excellent properties (absorbent properties) also in that the amount of wet back of the aqueous liquid after a long time elapsed is small, liquid diffusivity and stability with time of holding a constant amount of water (absorbing properties) are high.
  • the resulting water-containing gel like polymer was finely divided into around 5 mm.
  • the resulting finely divided water-containing gel-like polymer was placed on a wire netting of 300 ⁇ m sieve size (50 mesh) and dried under hot air at 150 °C for 90 minutes. Then, the resulting dried polymer was pulverized by a vibrating mill and further classified by a wire netting of 840 ⁇ m sieve size (20 mesh).
  • a precursor of the absorbing agent of undefined shape, an average particle diameter of 360 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 5 percent by weight was obtained.
  • the resulting absorbing agent has an average particle diameter of 360 ⁇ m, and the ratio of the particle with a particle diameter of less than 106 ⁇ m was 5 percent by weight.
  • results The results of the water absorbing agent by the centrifugal separation method and the diffusing absorbency under pressure (hereinafter simply referred to as results) of the water absorbing agent are shown in Table 5.
  • reaction solution To 5500g per weight of 39 percent by weight of sodium acrylate (neutralization rate 75 percent), dissolved was 3.59 g of trimethylolpropane triacrylate as a crosslinking agent to prepare a reaction solution. Next, a deairing operation of the reaction solution was performed for 30 minutes under an atmosphere of nitrogen. Next, to the same reaction vessel as the reaction vessel of the Example 16, the reaction solution was supplied, and the reaction system was displaced by introducing nitrogen gas while maintaining the reaction solution at 30 °C. Then, while agitating the reaction solution, 2.40 g of ammonium persulfate and 0.12 g of L-ascorbic acid were added to the reaction solution so as to start the polymerization, and a polymerization started after about 1 minute. The polymerization reaction was performed at 30 °C - 80 °C, and after leaving it for 60 minutes, a resulting finely divided water-containing gel-like polymer with a diameter of 5 mm was taken out.
  • the resulting finely divided water-containing gel-like polymer was placed on a wire netting of 300 ⁇ m sieve size (50 mesh) and dried under hot air at 150 °C for 90 minutes. Then, the resulting dried polymer was pulverized by a vibrating mill and further classified by a wire netting of 840 ⁇ m sieve size (20 mesh). As a result, a precursor of the absorbing agent of undefined shape, an average particle diameter of 400 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 3 percent by weight was obtained.
  • the resulting absorbing agent has an average particle diameter of 400 ⁇ m, and the ratio of the particle with a particle diameter of less than 106 ⁇ m was 3 percent by weight.
  • the results of the water absorbing agent are shown in Table 5.
  • reaction solution To 5500 g of 20 percent by weight of sodium acrylate, 2.35 g of N,N'-methylenebisacrylamide as a crosslinking agent was dissolved to prepare a reaction solution. Next, a deairing operation of the reaction solution was performed for 30 minutes under an atmosphere of nitrogen. Next, to the same reaction vessel as the reaction vessel of Example 16, the reaction solution was supplied, and the reaction system was displaced by introducing nitrogen gas while maintaining the reaction solution at 30 °C. Then, while agitating the reaction solution maintained at 30 °C, 1.5 g of ammnonium persulfate and 0.07 g of L-ascorbic acid were added to the reaction solution. As a result, a polymerization is started in about one minute.
  • the resulting water-containing gel-like polymer was finely divided into around 5 mm.
  • the resulting finely divided water-containing gel-like polymer was placed on a wire netting of 300 ⁇ m sieve size (50 mesh) and dried under hot air at 150 °C for 90 minutes. Then, the resulting dried polymer was pulverized by a vibrating mill and further classified by a wire netting of 840 ⁇ m sieve size (20 mesh).
  • a precursor of the absorbing agent of undefined shape, an average particle diameter of 390 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 4 percent by weight was obtained.
  • SP value: ⁇ 2.07 ⁇ 10 4 (J/m 3 ) 1/2 (10.1 (cal/cm 3 ) 1/2 )
  • 3 parts by weight of water and 0.75 part by weight of ethyl alcohol was mixed.
  • reaction solution To 5500 g of 39 percent by weight of sodium acrylate (neutralization rate 75 percent), dissolved was 7.18 g of trimethylolpropane triacrylate as a crosslinking agent to prepare a reaction solution. Next, a deairing operation of the reaction solution was performed for 30 minutes under an atmosphere of nitrogen. Next, to the same reaction vessel as the reaction vessel of Example 16, the reaction solution was supplied, and the reaction system was displaced by introducing nitrogen gas while maintaining the reaction solution at 30 °C. Then, while agitating the reaction solution maintained at 30 °C, 5.0 g of sodium persulfate and 0.25 g of L-ascorbic acid were added to the reaction solution. As a result, a polymerization is started in about one minute. During the polymerization process, temperature is maintained in a range of 30 °C - 80 °C. After leaving it for 60 minutes, the resulting water-containing gel-like polyhmer was taken out.
  • the resulting water-containing gel-like polymer was finely divided into around 5 mm.
  • the resulting finely divided water-containing gel-like polymer was placed on a wire netting of 300 ⁇ m sieve size (50 mesh) and dried under hot air at 150 °C for 90 minutes. Then, the resulting dried polymer was pulverized by a vibrating mill and further classified by a wire netting of 840 ⁇ m sieve size (20 mesh).
  • a comparative absorbing agent of undefined shape, an average particle diameter of 360 ⁇ m and ratio of particles having a diameter of 106 ⁇ m or below of 5 percent by weight was obtained.
  • the results of the resulting comparative absorbing agent are shown in Table 5.
  • a partially neutralized and crosslinked acrylate polymer (aquaric CA.W4; Nippon Shokubai Co., Ltd.) was used as a comparative absorbing agent.
  • the results of this comparative example are shown in Table 5.
  • a partially neutralized and crosslinked starch-acrylate graft polymer (Sunwet IM3900P; Hoechst Celanese Co., Ltd.) was used as a comparative absorbing agent.
  • the results of this comparative example are shown in Table 5.
  • a partially neutralized and crosslinked acrylate polymer (Diyawet US2-45Z; available from Mitsubishi Petrochemical Co., Ltd.) was used as a comparative absorbing agent. The results are shown in Table 5.
  • a partially neutralized and crosslinked acrylate polymer (Aquakeep SA-60; available from Sumitomo Seika Co., Ltd.) was used as a comparative absorbing agent. The results are shown in Table 5.
  • Example 22 The same operation as Example 22 was performed in the same manner except that absorbing agents obtained from Examples 17 and 18 were used in replace of the absorbing agent obtained from Example 16.
  • the results of the absorbent material are shown in Table 6.
  • Example 19 The same operation as Example 19 was performed except that the comparative absorbing agent obtained from Comparative Example 18 was used in replace of the absorbing agent obtained from Example 16.
  • the results of the comparative absorbent material are shown in Table 6.
  • Example 20 The same operation as Example 20 was performed except that the comparative absorbing agent obtained from Comparative Example 18 was used in replace of the absorbing agent obtained from Example 16.
  • the results of the comparative absorbent material are shown in Table 6.
  • Example 21 The same operation as Example 21 was performed except that comparative absorbing agent obtained from Comparative Example 18 was used in replace of the absorbing agent obtained from Example 16.
  • the results of the comparative absorbent material are shown in Table 6.
  • Example 22 The same operation as Example 22 was performed in the same manner except that comparative absorbing agents obtained from Comparative Examples 18-24 were used in replace of the absorbing agent obtained from Example 16.
  • the results of the comparative absorbent material are shown in Table 6. Diffusing absorbency under pressure of Absorbent material (g/g) after 30 min. after 60 min.
  • Example 19 19.4 19.7 Example 20 19.5 20.1 Example 21 19.3 22.2 Example 22 19.1 24.3 Example 23 19.4 23.1 Example 24 17.9 25.6 Comparative Example 25 17.6 18.5 Comparative Example 26 10.1 15.1 Comparative Example 27 9.6 14.2 Comparative Example 28 7.3 10.4 Comparative Example 29 13.0 16.9 Comparative Example 30 16.0 18.3 Comparative Example 31 7.4 10.7 Comparative Example 32 9.1 10.7 Comparative Example 33 11.5 15.8 Comparative Example 34 6.8 8.6
  • a so-called a back sheet made of polypropylene which is impermeable to liquid, a back sheet having a leg gather (liquid impermeable sheet), the absorbent material, the top sheet made of polypropylene which is permeable to liquid (liquid permeable sheet) are formed by laminating them using a both-sided tape.
  • the absorbent product a so-called paper diaper
  • the weight of the absorbent product was 46 g.
  • the absorbent product was mounted on a so-called Cupy doll (height 55 cm and weight 5 kg), and the doll is placed facing down. Then, a tube was inserted between the absorbent product and the doll, and 50 ml of physiological saline solution was injected each time into the portion corresponding to the portion from which urea is to be discharged at an interval of 20 minutes. Then, when the physiological saline solution was not absorbed in the absorbent product and leaking, the described injecting operation was ended, and the amount of the absorbed physiological saline solution was measured.
  • the average of the measurement was calculated, and the resulting value was determined as an absorbing amount. As a result, the absorbing amount of 250 g was obtained.
  • Example 25 The same reaction as Example 25 was performed in the same manner except that the comparative absorbing agent resulting from comparative example 18 was used in replace of the absorbing agent from Example 16.
  • the weight of the comparative absorbent product was 46 g.
  • Example 25 Using the comparative absorbent product, the same operation as Example 25 was repeated four times, and thereafter, the average of the resulting measurement value was calculated, and the value was determined as an absorbing amount. As a result, the absorbing amount of 255 g was obtained.
  • the absorbing agent and the absorbent material of the present invention has high diffusing absorbency under pressure and very high difusivility to liquid.
  • the difference in absorbent properties of the absorbing agent and the absorbent material between the present invention and comparative examples become greater as the resin concentration of the absorbent material becomes greater.
  • the absorbent property of the absorbent product of the present invention shows excellent properties (absorbent properties) such as very high absorbing amount (absorbing capacity) as compared to the comparative absorbent product.
  • the absorbing agent and the absorbent material are suitably applied essentially to thinner absorbent products such as a paper diaper, a sanitary napkin of higher performances, etc.
  • the present invention provides the absorbent products having excellent performances.

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Claims (34)

  1. Absorptionsmittel, erhältlich, indem durch Polymerisation einer ungesättigten monomeren Carbonsäure oder eines ihrer Salze eine Vorstufe des Absorptionsmittels hergestellt wird und der Teilchendurchmesser der Vorstufe so eingestellt wird, dass ein mittlerer Teilchendurchmesser im Bereich von 200 bis 600 µm erhalten wird und ein Anteil von bis zu 10 Gew.-% der Teilchen einen Teilchendurchmesser von weniger als 106 µm aufweisen, und die Vorstufe in Gegenwart eines Oberflächenvernetzungsmittels einer Wärmebehandlung unterworfen wird, so dass das Absorptionsmittel unter Druck eine Absorption durch Diffusion von nicht weniger als 30 g/g aufweist nachdem die Absorption für 60 Minuten durchgeführt worden ist, ausgedrückt als das Gewicht einer absorbierten physiologischen Kochsalzlösung pro Gewichtseinheit des Absorptionsmittels, wobei eine Belastung von 20 g/cm2 anliegt.
  2. Absorptionsmittel nach Anspruch 1, wobei das Monomer eine Acrylsäure und/oder ein Acrylsäuresalz als wesentlichen Bestandteil umfasst.
  3. Absorptionsmittel nach Anspruch 1 oder 2, welches nach 60 Minuten unter Druck eine Absorption durch Diffusion von nicht weniger als 32 g/g aufweist.
  4. Absorptionsmittel nach Anspruch 3, welches nach 60 Minuten unter Druck eine Absorption durch Diffusion von nicht weniger als 34 g/g aufweist.
  5. Absorptionsmittel nach einem der vorhergehenden Ansprüche, welches nach 30 Minuten unter Druck eine Absorption durch Diffusion von nicht weniger als 15 g/g aufweist.
  6. Absorptionsmittel nach Anspruch 5, welches nach 20 Minuten unter Druck eine Absorption durch Diffusion von nicht weniger als 15 g/g aufweist.
  7. Absorptionsmittel nach einem der vorhergehenden Ansprüche, wobei das Mittel einen Anteil an wasserlöslichen Bestandteilen von mehr als 0 bis zu 7 Gew.-% aufweist.
  8. Absorptionsmittel nach einem der vorhergehenden Ansprüche, wobei das Mittel weiter ein Dispersionsmittel enthält.
  9. Absorptionsmittel nach Anspruch 8, wobei das Dispersionsmittel in einer Menge von 0,005 Gewichtsteilen bis 0,5 Gewichtsteilen enthalten ist, bezogen auf 100 Gewichtsteile der Vorstufe des Absorptionsmittels.
  10. Absorbierendes Material, umfassend nicht weniger als 40 Gew.-% eines Absorptionsmittels gemäß einem der vorhergehenden Ansprüche, sowie eine hydrophile Faser.
  11. Absorbierendes Material nach Anspruch 10, wobei die hydrophile Faser in einer Menge von bis zu 60 Gew.-% enthalten ist.
  12. Absorbierendes Material nach Anspruch 10 oder 11, wobei das Absorptionsmittel in einer Menge von nicht weniger als 50 Gew.-% enthalten ist, bezogen auf die gesamte Menge des Absorptionsmittels und der hydrophilen Faser.
  13. Absorbierendes Material nach einem der Ansprüche 10 bis 12, wobei das Mittel weiter ein Bindemittel enthält.
  14. Absorbierendes Produkt, umfassend:
       eine absorbierende Schicht, welche ein absorbierendes Material gemäß einem der Ansprüche 10 bis 13 enthält, wobei das Material einen Anteil an wasserlöslichen Bestandteilen von mehr als 0 und bis zu 7 Gew.-% aufweist, und die absorbierende Schicht zwischen einer Lage angeordnet ist, die für Flüssigkeiten durchlässig ist und einer Lage, die undurchlässig für Flüssigkeiten ist.
  15. Absorbierendes Produkt nach Anspruch 14, wobei das absorbierende Material eine hydrophile Faser in einer Menge zwischen 20 und 40 Gew.-% enthält.
  16. Verfahren zur Herstellung einer Vorstufe eines Absorptionsmittels, umfassend den Schritt:
    Polymerisieren eines hydrophilen ungesättigten Monomers in wässriger Lösung, welches als Hauptbestandteil zumindest 50 Mol-% neutralisierte Acrylsäure enthält, in Gegenwart eines Dispersionsmittels, unter Verwendung eines Vernetzungsmittels, welches aus einer Hauptkomponente und einer hochsiedenden Komponente besteht, welche in einer Menge im Bereich von nicht weniger als 0,05 Mol-% und nicht mehr als 0,5 Mol-% enthalten ist, bezogen auf die gesamte Menge des hydrophilen ungesättigten Monomeren.
    wobei das Gewichtsverhältnis der Hauptkomponente des Vernetzungsmittels zur hochsiedenden Komponente im Bereich von 75/25 bis 99/1 gewählt ist,
    die Hauptkomponente des Vernetzungsmittels aus einer Esterverbindung zusammengesetzt ist, welche einen Polyhydroxyalkohol enthält, der nicht mehr als sechs Kohlenstoffatome und zumindest drei Hydroxygruppen aufweist, sowie einer ungesättigten Carbonsäure,
    das Verhältnis der Molekülgewichte der Hauptkomponente des Vernetzungsmittels zu einer Standardverbindung, bei der alle Hydroxygruppen des mehrwertigen Alkohols mit der ungesättigten Carbonsäure verestert sind, im Bereich von 0,7:1 bis weniger als 1,3:1 liegt, und
    die hochsiedende Komponente zumindest zwei Alkoholeinheiten pro Molekül enthält.
  17. Verfahren nach Anspruch 16, wobei das Gewichtsverhältnis der Hauptkomponente des Vernetzungsmittels zur hochsiedenden Komponente im Bereich von 80/20 bis 90/10 gewählt ist.
  18. Verfahren nach Anspruch 16 oder 17, wobei die Acrylsäure zwischen 65 Mol-% bis 80 Mol-% neutralisiert ist.
  19. Verfahren nach einem der Ansprüche 16 bis 18, wobei das Vernetzungsmittel in einer Menge im Bereich von 0,07 bis 0,2 Mol-% verwendet wird, bezogen auf das hydrophile ungesättigte Monomer.
  20. Verfahren nach einem der Ansprüche 16 bis 19, wobei das Dispersionsmittel in einer Menge im Bereich von 1 bis 100 Gew.-% verwendet wird, bezogen auf das Vernetzungsmittel.
  21. Verfahren nach einem der Ansprüche 16 bis 20, wobei während der Polymerisation in wässriger Lösung ein Schritt durchgeführt wird, in dem das Vernetzungsmittel und das Dispersionsmittel vermischt werden und die erhaltene Mischung in das hydrophile ungesättigte Monomer eingemischt wird.
  22. Verfahren nach einem der Ansprüche 16 bis 20, wobei die Polymerisation in wässriger Lösung die Schritte umfasst, in denen das Vernetzungsmittel, das Dispersionsmittel und die Acrylsäure vermischt werden, und die erhaltene Mischung in das hydrophile ungesättigte Monomer eingemischt wird.
  23. Verfahren nach einem der Ansprüche 16 bis 22, wobei der Polyhydroxyalkohol, welcher nicht mehr als sechs Kohlenstoffatome und zumindest drei Hydroxygruppen aufweist, Trimethylolpropan ist, und
       die ungesättigte Carbonsäure Acrylsäure ist.
  24. Verfahren zur Herstellung eines Absorptionsmittels, umfassend die Schritte:
    Einstellen der Vorstufe, welche durch das Verfahren nach einem der Ansprüche 16 bis 23 erhalten wurde, so dass diese einen Wassergehalt von nicht mehr als 10 %, einen mittleren Teilchendurchmesser im Bereich von 200 µm - 600 µm, und einen Anteil an Teilchen mit einem Durchmesser von nicht mehr als 106 µm von nicht mehr als 10 Gew.-% aufweist; und
    Durchführen einer Wärmebehandlung der Vorstufe in Gegenwart eines Oberflächenvernetzungsmittels.
  25. Verfahren nach Anspruch 24, wobei die Wärmebehandlung bei einer Temperatur im Bereich von 80 bis 250 °C durchgeführt wird.
  26. Verfahren nach Anspruch 24, wobei das Oberflächenvernetzungsmittel aus einem ersten Oberflächenvernetzungsmittel aufgebaut ist, das mit einer Carboxylgruppe reagiert, welche einen Löslichkeitsparameter (SP-Wert) von nicht weniger als 2,56 x 104 (J/m3)1/2 (12,5 cal/cm3)1/2) aufweist und einem zweiten Oberflächenvernetzungsmittel, das einen Löslichkeitsparameter von weniger als 2,56 x 104 (J/m3)1/2 (12,5 cal/cm3)1/2) aufweist: und
       die Wärmebehandlung bei einer Temperatur von nicht weniger als 160 °C durchgeführt wird.
  27. Verfahren zur Herstellung eines Absorptionsmittels, umfassend die Schritte:
    Vermischen einer Vorstufe eines Absorptionsmittels, das Carboxylgruppen umfasst, mit einem ersten und einem zweiten Oberflächenvernetzungsmittel. welche mit Carboxylgruppen reagieren, wobei die Vorstufe eine undefinierte Gestalt aufweist, einen mittleren Teilchendurchmesser von 200 µm - 600 µm sowie einen Anteil von Teilchen mit einem Durchmesser von nicht mehr als 106 µm von bis zu 10 Gew.-%, wobei das erste Oberflächenvernetzungsmittel einen Löslichkeitsparameter von nicht weniger als 2,56 x 104 (J/m3)1/2 (12,5 cal/ cm3)1/2) aufweist, das zweite Oberflächenvernetzungsmittel einen Löslichkeitsparameter von weniger als 2,56 x 104 (J/m3)1/2 (12,5 cal/cm3)1/2) aufweist; und
    Durchführen einer Wärmebehandlung, so dass ein Absorptionsmittel erhalten wird, das nach Ablauf von 60 Minuten unter Druck eine Absorption durch Diffusion von nicht weniger als 30 g/g aufweist.
  28. Verfahren nach Anspruch 27, wobei die Wärmebehandlung bei einer Temperatur im Bereich von 160 - 250 °C durchgeführt wird.
  29. Verfahren nach Anspruch 27 oder Anspruch 28, wobei nach Ablauf von 60 Minuten unter Druck die Absorption durch Diffusion nicht weniger als 32 g/g beträgt, wenn sie nach Ablauf von 60 Minuten gemessen wird.
  30. Verfahren nach einem der Ansprüche 27 bis 29, wobei das erste Oberflächenvernetzungsmittel zumindest eine Verbindung ist, die aus der Gruppe ausgewählt ist, welche besteht aus Ethylenglykol, Propylengylkol, Glycerin, Pentaerythritol, Sorbitol, Ethylcarbonat, und Propylencarbonat.
  31. Verfahren nach einem der Ansprüche 27 bis 30, wobei das Absorptionsmittel einen wasserlöslichen Anteil von mehr als 0 und bis zu 7 Gew-.% aufweist.
  32. Absorptionsmittel nach einem der Ansprüche 1 bis 9, welches erhalten wird, indem eine Vorstufe eines Absorptionsmittels in Gegenwart eines ersten Oberflächenvernetzungsmittels, das mit Carboxylgruppen reagiert und einen Löslichkeitsparameter (SP) von 2,56 x 104 (J/m3)1/2 (12,5 cal/cm3)1/2) oder größer aufweist, und eines zweiten Oberflächenvernetzungsmittels, das mit Carboxylgruppen reagiert und einen Löslichkeitsparameter (SP) von weniger als 2,56 x 104 (J/m3)1/2 (12,5 cal/cm3)1/2) aufweist, einer Wärmebehandlung unterzogen wird.
  33. Verfahren zur Herstellung eines absorbierenden Materials, umfassend die Schritte:
       Vermischen eines Absorptionsmittels, das mit dem Verfahren nach einem der Ansprüche 24 bis 31 erhalten wurde, mit einer hydrophilen Faser, wobei der Anteil des Absorptionsmittel nicht weniger als 40 Gew.-% beträgt.
  34. Verfahren nach Anspruch 33, wobei zumindest das Absorptionsmittel und die hydrophile Faser in der Weise vermischt werden, dass der Anteil des Absorptionsmittels nicht weniger als 50 Gew.-% beträgt.
EP95921136A 1994-06-13 1995-06-09 Wasser-absorbent, verfahren zu dessen herstellung und den enthaltender absorbent-gegenstand Revoked EP0712659B1 (de)

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Application Number Priority Date Filing Date Title
JP13038594 1994-06-13
JP130385/94 1994-06-13
JP13038594 1994-06-13
JP132126/94 1994-06-14
JP13212694 1994-06-14
JP13212694 1994-06-14
PCT/JP1995/001150 WO1995034377A1 (fr) 1994-06-13 1995-06-09 Produit absorbant l'eau, son procede de production, et article absorbant le renfermant

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EP0712659A1 EP0712659A1 (de) 1996-05-22
EP0712659A4 EP0712659A4 (de) 1996-12-27
EP0712659B1 true EP0712659B1 (de) 2002-01-09

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US (3) US5760080A (de)
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EP3437732B1 (de) 2016-03-28 2022-05-11 Nippon Shokubai Co., Ltd. Teilchenförmiges wasserabsorbierendes mittel

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KR0183511B1 (ko) 1999-04-15
EP0712659A4 (de) 1996-12-27
DE69524928D1 (de) 2002-02-14
WO1995034377A1 (fr) 1995-12-21
US5760080A (en) 1998-06-02
US6180724B1 (en) 2001-01-30
EP0712659A1 (de) 1996-05-22
KR960703352A (ko) 1996-08-17
DE69524928T2 (de) 2002-08-29
US6054541A (en) 2000-04-25

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